Bis(benzoxazolyl)thiophene compounds



FIP83U9 XR.

United States Patet O 3,135,762 BIS (BENZOXAZOLYL)THIOPHENE COMPOUNDS Erwm Maeder, Muenchenstein, Peter Liechti, Binningen,

Max Duennenberger, Birsfelden, and Adolf Emil Siegrlst, Basel, Switzerland, assignors to Ciba Limited,

Basel, Switzerland, a company of Switzerland No Drawing. Filed Jan. 10, 1962, Ser. No. 165,315

Claims priority, application Switzerland J an. 19, 1961 6 Claims. (Cl. 260-307) The present invention provides new valuable derivat1ves of thiophene corresponding to the general formula Ya \Jiil/ 1 Y 1 2 where Y, represents a saturated non-aromatic hydrocarbon radical with at most 12 carbon atoms and Y a hydrogen or chlorine atom or a saturated non-aromatic hydrocarbon radical with at most 12 carbon atoms and Y and Y together contain at least 4 carbon atoms; and Z and Z may be identical or dilferent and each represents a hydrogen atom or a hydrocarbon radical with 1 to 10 carbon atoms, for example a methyl, ethyl, tertiary butyl, phenyl, tolyl, benzyl or cyclohexyl group.

As saturated non-aromatic hydrocarbon radicals there may be mentioned the straight-chain or branched alkyl groups of the formula 4 nooc-a-coorr where R represents a thiophene radical bound in positions 2 and 5 to the carboxyl groups, or by reaction with a functional derivative of said dicarboxylic acid, using an ortho-hydroxybenzene of the formula 3,135,762 Patented June 2, 1964 where X, represents a non-aromatic hydrocarbon radical with at most 22 carbon atoms and X represents a hydrogen or chlorine atom or a non-aromatic hydrocarbon radical with at most 22 carbon atoms and X and X together contain at least 4 carbon atoms.

Particularly suitable starting materials are, for example, the ortho-hydroxyaminobenzenes that contain as further substituent a saturated, non-aromatic hydrocarbon radical with at least 2, for example 4, 6-, 8 or 12, carbon atoms. As examples there may be mentioned 1-amino-2-hydroxy- 5-alkylbenzenes corresponding to the formula CH C Ha-CH: NH:

(12) Hal mo-h- NH2 acid of the Formula 4, for example thiophene-ZzS-dicarboxylic acid, 3:4- dimethylthiophene-2:S-dicarboxylic acid, 3:4-diphenylthiophene-2:S-dicarboxylic acid or monomethylor monophenyl-thiophene-Z:S-dicarboxylic acid, or a functional derivative of said dicarboxylic acids, for example a dinitrile or an ester. Particularly suitable esters are those with lower aliphatic alcohols, for example the dimethyl or diethyl ester.

The reaction of the components concerned is carried out by-heating them at elevated temperatures, for example at 160 to 260 C., advantageously in an inert gas, for example nitrogen. It is of advantage to perform the reaction in the presence of a catalyst. Suitable catalysts are for example, boric acid, zinc chloride, para-toluenesulfonic acid, also polyphosphoric acids including pyrophosphoric acid. When the reaction is performed with boric acid as catalyst, it is of advantage to use the acid in an amount of about 0.5 to calculated on the total weight of the reaction batch. It is possible to use concomitantly high-boiling polar organic solvents, for ex ample dimethyl formamide or aliphatic, optionally etherified, hydroxyl compounds, for example propylene glycol, ethylene glycol monoethyl ether or diethylene glycol diethyl ether.

The new thiophene derivatives of the composition defined above display in the dissolved or finely dispersed state a more or less distinct fluorescence. They can be used for optically brightening a wide variety of materials, more especially organic materials. Good results are achieved, for example, in brightening acrylic resin lacquers, alkyd resin lacquers, cellulose ester lacquers, for example acetylcellulose lacquers or nitrocellulose ester lacquers. The new thiophene derivatives are particularly suitable for optically brightening synthetic fibers, for example fibers of cellulose esters such as cellulose propionate or acetylcellulose (cellulose diacetate or triacetate; acetate rayon) polyamides (for example nylon) or fibers or polyolefines such as polyethylene or polypropylene, as well as films, foils, tapes or shaped structures of these materials or other materials such as polystyrene, polyvinyl alcohol or polyvinyl esters of organic acids, for example polyvinyl acetate.

If it is desired to optically brighten by the present process synthetic fibers, which may be in the form of staple fibers or monofils, in the crude state, in the form of hanks or fabrics, it is of advantage to work in an aqueous suspension of the compounds concerned. If desired there may be further added to the treatment bath a dispersing agent such, for example, as a soap, a polyglycol ether of a fatty alcohol, fatty amines or alkylphenols, cellulose sulfite waste liquor or condensation products of optionally alkylated naphthalenesulfonic acids with formaldehyde. It is particularly advantageous to Work in a neutral, weakly alkaline or acidic bath. Likewise, it is of advantage to perform the treatment at an elevated temperature ranging from about 50 to 100 C.,

for example at the boiling temperature of the bath or in its vicinity (about 90 C.). The improvement according to the present process may also be carried out with solutions in organic solvents.

Furthermore, the new thiophene derivatives to be used according to this invention may also be added to, or incorporated with, the materials to be brightened before or during the shaping of the latter.

added to the moulding composition facture. of films, foils, tapes or shaped may be dissolved or finely dispersed in before the spinning operation. The

Thus, they may be during the manuproducts, or they the spinning mass new thiophene derivatives mayalso be added to the reaction mixture be- Even a very small amount-in certain cases for example 0.0l%will produce a distinct and durable effect, but it is also possible to use an amount of up to about 2%.

The new thiophene derivatives serving as brightening agents may also be used as follows:

(a) In admixture with dyestuffs or pigments or as additives to dyebaths, printing, discharge or resist pastes. Furthermore, for after-treating dyeings, prints or discharge effects.

(b) In admixture with chemical bleaches or as additives to bleaching baths.

(0) In admixture with finishing agents such as starch or synthetically produced finishing agents. The products of the invention may also be added, for example, to liquors used for producing a crease-resistant finish.

(d) In combination with detergents. The detergent and the brightening agent may be added separately to the liquors used. It is also advantageous to use a detergent in the form of a mixture with a brightening agent. Suitable detergents are, for example, soaps, salts of sulfonate detergents, such for example as sulfonated benzimidazoles substituted by higher alkyl radicals at carbon atom 2; furthermore salts of monocarboxylic acid esters of 4-sulfophthalic acid with higher fatty alcohols; furthermore salts of fatty alcohol sulfonates, alkyl-aryl sulfonic acids or condensation products of higher fatty acids with aliphatic hydroxysulfonic or aminosulfonic acids. Furthermore there may be used non-ionic detergents, for example polyglycol ethers derived from ethylene oxide and higher fatty alcohols, alkyl phenols or fatty amines.

When the present process is combined with other treatment or improving methods, the combined treatment is advantageously performed with the aid of a suitable preparation. These stable preparations contain compounds of the above Formula 1 as well as dispersing agents, detergents, dyestuifs, pigments or finishing agents. The compounds of the above Formula 1 may also be used fixed on a finely dispersed substratum.

Unless otherwise indicated, parts and percentages in the following examples are by weight.

EXAMPLE 1 A mixture of 370 parts of 1-hydroxy-2-amino-4-(l' methyl-propyl)-benzene, 172 parts of thiophene-ZrS-dicarboxylic acid and 6 parts of boric acid is heated for 1 /2 hours in an oil bath under nitrogen at 230 C., during which water escapes and a homogeneous melt is formed. After cooling to below C., 2000 parts by volume of ethanol are added, whereby at an elevated temperature a dark solution is obtained which is stirred into 10,000 parts by volume of sodium hydroxide solution of 4% strength. The precipitate formed is suctioned otf, washed with water until the washings run neutral and covered with methanol. After drying there are obtained about 343 parts of the compound of the formula O, H, percent percent CzgHggNgOgS:

Calculated 72. 53 6. 09 Found 72. 42 6. 23

The compound of the Formula 15 canbe used for opti- The compounds of the Formulae 18 to 24 can be used for optically brightening, for example, acetyl-cellulose or polyethylene.

EXAMPLE 3 8.6 parts of thiophene-Z:S-dicarboxylic acid with 151 parts of 3-amino-4-hydroxy-l-n-propylbenzene in 1000 parts of 1:2-propylene glycol are heated with stirring in an oil bath to 160 C. under nitrogen. 2 parts of anhydrous zinc chloride are added to the resulting solution and the bath temperature is raised so that within 6 hours 900 parts of propylene glycol pass over together with the eliminated water. The mixture is then cooled to below 110 C. and 400 parts of formic acid are dropped in. The precipitate formed is suctioned 01f at room temperature and washed with a small amount of methanol. After drying there are obtained about 115 parts of the compound of the. formula in the form of a yellowish powder melting at 149.5 to 150.5 C.

On recrystallization from ethanol there are obtained very fine, pale-yellow needles melting at 151 C., which display the following analytical data:

C, H, N, percent percent percent CuHnNgOgS! The compound of the Formula 25 can be used for optically brightening polyethylene.

EXAMPLE 4 A mixture of 6 parts of 3 :4-dimethyl-thiophene-2:5-di- 'carboxylic acid, 12.5 parts of 1-hydroxy-2-amino-4-tertiary butylbenzene and 0.5 part of boric acid is heated in 'an oil bath at 230 to 240 C. for 1 /2 hours under ni- (26) H C H in the form of a beige powder melting at 236 to 236.5 C. Recrystallization from chlorobenzene-l-ethanol yields small, yellowish, felted needles melting at 237 to 237.5 C.

C, H, N, percent percent percent czsHaoNzoz l Calculated 73.33 6.59 6.23 Found 73.38 6. 64 6.11

When in this example 1-hydroxy-2-arnino-4-tertiary butyl-benzene is replaced by an equivalent amount of 1 hydroxy 2 amino-4-ethylbenzene and analogous condensation is performed, an approximately identical yield is obtained of the compound of the formula (27) I CH3 in small, yellowish needles melting at 195 to 196 C. from dioxane.

C H N ozlHazNzoz i Calculated 71. 61 5. 51 6. 96 Found 71. 49 5. 51 7. 07

in the form of a yellowish resin, which does not flow at room temperature, after repeated chromatography on alumina.

C H N CuHazNzOz r Calculated 77. 37 9. 18 4. 10 Found 77. 35 9. 30 3. 82

The compounds of the Formulae 26, 27 and 28 can be used for optically brightening polyethylene.

EXAMPLE 5 6 parts of 3:4-dimethyl-thiophene-2:5-dicarboxylic acid and 9 parts of 1-hydroXy-2-amino-4-n-propyl-benzene in 50 parts by volume of 1:2-propylene glycol are heated with stirring to C. in an oil bath under nitrogen, to yield a clear solution. 1.5 parts of anhydrous zinc chloride are added and the temperature of the boil bath is raised to a degree such that within 6 hours 45 parts of propylene glycol pass over together with the water of reaction formed.

20 parts by volume of concentrated formic acid are then dropped into the reaction mixture. After cooling to room temperature the precipitate is suctioned off and washed with methanol.

After drying there are obtained about 5 parts of the compound of the formula in the form of a yellow powder melting at 179 to'- On recrystallization from dioxane-i-ethanol it forms yellowish prisms melting at 180 to 1805 C.

1 percent percent percent O26H20N2O2S1 Calculated 72. 53 6.09 6. 51 Found 72. 60 6. 10 6. 53

The new compound can be used for optically brightening polyethylene.

EXAMPLE 6 6.5 parts of 3:4-dipheny1-thiophene-2:S-dicarboxylic acid are mixed with 10 parts of 1-hydroxy-2-amino-4- tertiary butyl-benzene and 0.2 parts of boric acid, and the whole is heated under nitrogen in an oil'bath for 1 /2 hours at 250 C., during which water escapes and a clear melt is formed which is dissolved in 15 parts by volume of dimethylformamide. 35 parts by volume of ethanol are added, the whole is cooled to room temperature, suction-filtered and washed with methanol. After drying there are obtained about 10 parts of the compound of the formula r in the form of a yellow powder which melts at 255 to 258 C.; after recrystallization from chlorobenzene+eth-- anol it forms small yellow needles melting at 262.5 to' O, H, N, percent percent percent Caa a4N2O2 Calculated 78. 32 5. 88 4. 81 Found 78. 41 5. 90 4. 78

The compound of the Formula 30 can be used, for example, for optically brightening polyethylene.

By a similar reaction of 24.8 parts of 3-phenylthio phene-2:5-dicarboxylic acid, 38 parts of 1-hydroxy-2- amino-4-tertiary butyl-benzene and 1 part of boric acid a there is obtained the compound of the formula 13 C CH3 Yield: 25 parts of a yellow crystalline powder which melts at 176.5 to 178.5 C.; after recrystallization from cyclohexane it forms a light-yellow finely crystalline powder melting at 179 to 180 C.

0.115 mol each of the compounds 31 and 12, or of the compounds 31 and 33 or of the compounds 31 and 14, or the compounds 32 and 12, are intimately mixed with 0.1 mol of thiophene-ZzS-dicarboxylic acid and 1 gram of boric acid, heated within about 45 minutes to 240 to 250 C. and stirred at this temperature for about 2 hours, during which water distils 011. The melt is comminuted, extracted with '200 to 400 cc. of hot carbon tetrachloride and the extract is separated into its constituents on alumina of the chromatographic activity stage 1 (according to Brockmann).

By using as eluant carbon tetrachloride, methylene chloride, chloroform and mixtures thereof, there are obtained in addition to resinous, colored vby-products in each case substantially 2 symmetric products and a symmetric product of the formulae shown in Table I.

Table I No. Compound obtained Analysis and purification Meltiig pom N N C H N i li OC\ /O-C galcuated 216-217C.

. oun s 4 x perehloroethylene N N o H N 77 ocrn (3-0 GC (1H3 70.56 4.85 7.48 188189 o. Found.-." 70.19 4.80 7.30 \O I S O 4 x perchloroethylene Table IContinued NO- Compound obtained Analysis and purification Melting pom N N H N HOOH H [l H E Calculated "72.53 6.09 199200 0. H3O /CC\ /GC\ Found .72.73 6.17 5

O 0 CH3 3 X dioxane ethanol /N HG CH N o :1 N u n o /CC\ /OO\ galcuated is: 2 136-137 0.

I CHS GIH OHZ OH3 4 x perohloroethylene /N HO OH N\ 0 H N 1| u /C-C*\ /C-C\ galcuated 14 1-1445 0.

l CH3CH;-CHGH3 OH2 CH CH2 CH3 3 x oyciohexane N N 0 H N 37.-.. fi (FH -C12 z5 /00\ /CG\ galouated 3 4. 7.04 5.52 97-99 0.

min G. 97 5. S

4 x petroleum ether N N 0 H N 21-... H150 fi fi C1zHn5 C- /O-C galcuated 8. 93 3.28 Yellowish un .5 9.1 .26 resinous S 0 product 0 0 after repeated chromatography on alumina.

/N HG CH N o n N 38.... O1 -C1 C-O OC Calculated 55. 83 2.08 7.23 297-299 O. Found 56.21 1.94 7.33

3xdioxane H 0 39 H o-( 1- HCCH 0i 0 H N a I u I H3O 0-0 00 Calculated 64.62 4.19 7.84 22o-227 O. Found "64.48 4.18 7.80

3 x porchloroethylene The Yields and ehlants are listed in Table IL 35, 34, or 23, 36, 34 or 21, 37, 34 can be used as optical Table II bigliltellers for polyamides, acetylcellulose and polye yene. o-Amino- Resulting Yield EXAMPLE 8 p E t Polypropylene fibers are treated at a goods-to-llquor g g 'flg fi 0 In In ratio of 1:40 With 0.1% of the compound of the Formula 7 formula for ula grams percent 18 for 60 minutes at 60 to 100 C. in a bath containing, per liter, 5 grams of an addnct of about 35 mols of g g gg-g ethylene oxide With 1 mol of octadecyl alcohol, and 0.5 (34) gram of trisodinm phosphate. The material is then C 01 CH 3-3 2% rinsed and dried. The polypropylene fibers treated as ,(34) ,13 1 1 described possess a substantially higher white content (21) 0 4 than the untreated fibers 37 CHO 5!.0 45.0 E34; (mink 3.1 13.5 When 1 gram of formlc acid of 85% strength is used fi throughout Wlt instead of 0.5 gram of trisodium phosphate, a similar (39; On extracting the eluate 2.3 5.6 result is obtained. 38 with C01, compound of formula (3 9) is left. EXAMPLE 9 Polyethylene fibers are treated at a goods-to-liquor ratio The compounds of the Formulae 35, 36, 37 and 39 and the mixtures of the compounds of the Formulae 18,

liter, grams of an adduct of about 35 mols of ethylene stead of the compound of the Formula 29 or 27 an equal oxide with 1 mol of octadecyl alcohol, and 0.5 gram of amount of the compound of the Formula 26 or 30. trisodium phosphate. The material is then rinsed and dried. The polyethylene fibers treated as described EXAMPLE 13 possess a substantially higher white content than the 5 Acetylcellulose fibers are treated at a goods-to-liquor untreated fibers. ratio from 1:10 to 1:40 with 0.02 to 0.2% of 2:5-di-[5'- When 1 gram of formic acid of 85% strength is used tertiary butyl-benzoxazoly1-( ')lp fif 0f the instead of 0.5 gram of trisodium phosphate, a similar e 18 f r 60 minu es at 60 to 100 C. in a bath conresult is obtained. taining, per liter, 1 gram of an adduct of about 35 mols LE 0 of ethylene oxide with 1 mol of octadecyl alcohol. EXAMP 1 After having been rinsed in cold water and dried, the

100 parts of polyethylene (Al at e e W are acetylcellulose fibers possess a substantially higher white rolled on a warm calender to form a homogeneous foil. content than the untreated fib 0.02 part of the compound of the Formula 19 is worked EXAMPLE 14 t thi il. T if m o 8 f0 he m1 is Pulled the calender and 5 A solution of 0.05 to 0.2 part of 2:5-di-[5-tertiary then pressed between steel platens heated at 130 to 135 butyl benzoxazolyl thiophene of the Formula 18 in C.t thth f 1 1211 d ig gg s i 3,3 zgs in this manner hot acetone or dimethyl formamide is added to an acetylpossesses a substantially higher white content than a foil celll/ulose spmmngdsogmon of 2 Parts of if f t t which does not contain the compound of the Formula 19. i 2 3 i g o F g e mtxture 5 When the compound of the Formula 19 is replaced by mtunate Y Sun an en spun mto aments m usu an equal amount of the compound of the Formula or manner of the compound of the Formula 27, simliar brightening T respltmg filaments possess a Substantially hlgher effects are achieved white content than filaments that do not contain the compound of the Formula 18.

EXAMPLE 11 25 What is claimed is: 100 parts of polyethylene (Alkathene WNG 14) are 1. The compound of the formula rolled on a warm calender to form a homogeneous foil. 0 N N CH 0.02 to 0.08 part of the compound of the Formula 18 HC--CH a and 0.5 part of titanium dioxide are worked into the foil. l 9 The foil is then pulled ofi the calender and pressed E CH3 between steel platens at 130 to 135 C. to smooth the foil 0 S O on both sides.

The resulting opaque polyethylene foil possesses a sub- The compound of the formula stantially higher white content than a foil that does not 35 N N contain the compound of the Formula 18. 0 -0- \C E E G/ CCH3 EXAMPLE 12 Ha HS s parts of polyethylene (Alkathene WNG 14) are 0 0 rolled on a calender at C. to form a homogeneous 3. The compound of the formula fine-CH GHQ-CH2 N HO---CH n,o no 1,: J on /CH2 M46. out-on. 0 S o foil. 0.02 part of the compound of the Formula 29 or 4. The compound of the formula of the compound of the Formula 27 is then slowly worked N N into the foil. After 5 minutes the foil is taken off the HC--OH calender and pressed to form a panel on a press heated 50 P at 130 to C.

The resulting polyethylene material possesses a sub- 0 S O stantially higher White content than a comparable mate- E CHSAEEFCHFCHa rial that does not contain the compound of the Formula 29 or 27. I 5. The compound of the formula CH N N EH ca om-inn \o ifj i jo/ HCHz-CH \s Similar brightening efiects are achieved by using in- 6. The compound of the formula CH CH CH CH N N oH,-hortzhg 3 h-om-h-on on. but s (in. $11, '0 0 References Cited in the file of this patent UNITED STATES PATENTS 2,985,661 Hein et a1. May 23, 1961 2,995,564 Dnennenberger et al Aug. 8, 1961 2,995,605 Siegrist et a1. Aug. 8, 1961 FOREIGN PATENTS 1,179,825 France Dec. 22, 1958 Mn "7 View r UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3 135,762 June 2., 1964 Erwin Maeder et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, lines 13 to 18 for that portion of the formula reading:

\ N/ read X1 m columns 9 and 10, Table I formula Noe 35 for that portion of the formula reading:

CH CH 3 I 3 -C CH3 read C CH3 CH CH column 14 line 22 for "resplting read resulting Signed and sealed this 3rd day of November 1964a (SEAL) Attest:

ERNEST W, SWEDER EDWARD J, BRENNER Attesting Officer Commissioner of Patents 

1. THE COMPOUND OF THE FORMULA
 3. THE COMPOUND OF THE FORMULA 